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Benzyl methacrylate (BzMA) is polymerized using a poly(lauryl methacrylate) macromolecular chain transfer agent (PLMA macro-CTA) using reversible addition–fragmentation chain transfer (RAFT) polymerization at 70 °C in n-dodecane. This choice of solvent leads to an efficient dispersion polymerization, with polymerization-induced self-assembly (PISA) occurring via the growing PBzMA block to produce a range of PLMA–PBzMA diblock copolymer nano-objects, including spheres, worms, and vesicles. In the present study, particular attention is paid to the worm phase, which forms soft free-standing gels at 20 °C due to multiple inter-worm contacts. Such worm gels exhibit thermo-responsive behavior: heating above 50 °C causes degelation due to the onset of a worm-to-sphere transition. Degelation occurs because isotropic spheres interact with each other much less efficiently than the highly anisotropic worms. This worm-to-sphere thermal transition is essentially irreversible on heating a dilute solution (0.10% w/w) but is more or less reversible on heating a more concentrated dispersion (20% w/w). The relatively low volatility of n-dodecane facilitates variable-temperature rheological studies, which are consistent with eventual reconstitution of the worm phase on cooling to 20 °C. Variable-temperature 1H NMR studies conducted in d26-dodecane confirm partial solvation of the PBzMA block at elevated temperature: surface plasticization of the worm cores is invoked to account for the observed change in morphology, because this is sufficient to increase the copolymer curvature and hence induce a worm-to-sphere transition. Small-angle X-ray scattering and TEM are used to investigate the structural changes that occur during the worm-to-sphere-to-worm thermal cycle; experiments conducted at 1.0 and 5.0% w/w demonstrate the concentration-dependent (ir)reversibility of these morphological transitions.

ABSTRACT. Well-defined poly(lauryl methacrylate-benzyl methacrylate) (PLMA-PBzMA) diblock copolymer nanoparticles are prepared in n-heptane at 90°C via reversible addition-fragmentation chain transfer (RAFT) polymerization. Under these conditions, the PLMA macromolecular chain transfer agent (macro-CTA) is soluble in n-heptane, whereas the growing PBzMA block quickly becomes insoluble. Thus this dispersion polymerization formulation leads to polymerization-induced self-assembly (PISA). 10Using a relatively long PLMA macro-CTA with a mean degree of polymerization (DP) of 37 or higher leads to the formation of well-defined spherical nanoparticles of 41 to 139 nm diameter, depending on the DP targeted for the PBzMA block. In contrast, TEM studies confirm that using a relatively short PLMA macro-CTA (DP = 17) enables both worm-like and vesicular morphologies to be produced, in addition to the spherical phase. A detailed phase diagram has been elucidated for this more asymmetric diblock 15 copolymer formulation, which ensures that each phase can be targeted reproducibly.1 H NMR spectroscopy confirmed that high BzMA monomer conversions (> 97 %) were achieved within 5 h, while GPC studies indicated that reasonably good blocking efficiencies and relatively low diblock copolymer polydispersities (M w /M n < 1.30) were obtained in most cases. Compared to prior literature reports, this allmethacrylic PISA formulation is particularly novel because: (i) it is the first time that higher order 20 morphologies (e.g. worms and vesicles) have been accessed in non-polar solvents and (ii) such diblock copolymer nano-objects are particularly relevant to potential boundary lubrication applications for engine oils.

There is considerable current interest in polymerization-induced self-assembly (PISA) via reversible addition-fragmentation chain transfer (RAFT) polymerization as a versatile and efficient route to various types of block copolymer nano-objects. Many successful PISA syntheses have been conducted in water using either RAFT aqueous dispersion polymerization or RAFT aqueous emulsion polymerization. In contrast, this review article is focused on the growing number of RAFT PISA formulations developed for non-aqueous media. A wide range of monomers have been utilized for both the stabilizer and core-forming blocks to produce diblock copolymer nanoparticles in either polar or non-polar solvents via RAFT dispersion polymerization. Such nanoparticles can exhibit spherical, worm-like or vesicular morphologies, often with controllable size and functionality. Detailed characterization of such sterically-stabilized diblock copolymer dispersions provide important insights into the various morphological transformations that can occur both during the PISA synthesis and also subsequently on exposure to a suitable external stimulus (e.g. temperature).

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In situ SAXS studies reveal the evolution of copolymer morphology during the PISA synthesis of diblock copolymer nano-objects in mineral oil.

Diblock copolymer spheres, worms and vesicles are prepared via RAFT dispersion polymerization of benzyl methacrylate in either mineral oil or a poly(α-olefin) using polymerization-induced self-assembly; an efficient ‘one-pot’ protocol is reported for spheres at 30% solids in mineral oil.

Thermo-responsive vermicious (or worm-like) diblock copolymer nanoparticles prepared directly in n-dodecane are used to stabilise water-in-oil Pickering emulsions.